TW202334173A - Blended composition and uses thereof - Google Patents

Abstract

Synthesis reactions are described to efficiently and specifically form compounds of the structure RSnZ3, where R is an organic ligand to the tin, and Z is hydrolysable ligand or a hydrolysis product thereof. The synthesis is effective for a broad range of R ligands. The synthesis is based on the use of alkali metal ions and optionally alkaline earth (pseudo-alkaline earth) metal ions. Compounds are formed of the structures represented by the formulas RSn(C ≡ CSiR'3)3, R'R"ACSnL3, where A is a halogen atom (F, Cl, Br or I) or an aromatic ring with at least one halogen substituent, R'R"(R'"O)CSnZ3 or R'R"(N ≡ C)CSnZ3.

Description

Blend compositions and their applications

The present invention relates to an improved method for producing mono-organotin triamide and mono-organotin triacetylide, wherein the organic group is defined as a hydrocarbon group with or without one or more heteroatoms.

Organometallic compounds provide metal ions for film deposition in solution-processable and gas-phase forms. Organotin compounds provide radiation-sensitive Sn-C bonds that can be used to pattern films lithographically. Fabricating semiconductor devices at ever-shrinking dimensions requires new versatile materials to achieve the required patterning resolution; organotin compounds are expected to provide the required patterning advantages.

In one aspect, the invention relates to a solution comprising an organic solvent; and an organometallic composition dissolved in the solvent. The organic metal composition includes alkali metal ions, tin ions, and organic ligands bonded to tin as -SnL ₃ , wherein the organic ligands (L) are composed of -NR' ₂ , -C≡CR ^s , Or a mixture thereof, wherein R ^s is SiR" _or R', the three R" are independently H or R', and R' is independently having 1 to 31 carbon atoms and optional unsaturated carbon-carbon bonds, optional aromatic groups, and optionally heteroatom hydrocarbon groups. In some embodiments, the organic metal composition further includes alkaline earth metal ions (Be (+2), Mg (+2), Ca (+2), Sr (+2), Ba (+2)) or pseudo Alkaline earth (pseudo-alkaline earth) metal ions (Zn (+2), Cd (+2), or Hg (+2/+1)).

In another aspect, the invention is directed to a method of forming an alkali metal tin composition, wherein the method includes making ML, tin(II) halide (SnX ₂ , X=F, Cl, Br, I, or mixtures thereof) , and optionally M'OR ⁰ is reacted in an organic solvent, wherein M is Li, Na, K, Cs, or a combination thereof, M' is Na, K, Cs, or a combination thereof, and L is a dialkylamine (dialkylamide) ( _-NR ' ₂ ) or acetylide (-C≡CR ^s ) to form corresponding organometallic compositions with a SnL ₃ moiety, which is tin triamine (Sn(NR' ₂ ) ₃ ) or tin triacetylide (Sn(C≡CR ^s ) ₃ ), present with an associated metal cation M", where M" is M' if M' is present, or M" is M if M' is not present , R ⁰ is a hydrocarbon group having 1 to 31 carbon atoms and optional unsaturated carbon-carbon bonds, optional aromatic groups, and optional heteroatoms, R ^s is SiR" ₃ or R', three R" is independently H or R', and R' is independently a hydrocarbon group having 1 to 31 carbon atoms and optionally an unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom, To form an alkali metal tin composition. In some embodiments, the method further includes making an (alkaline earth/pseudo-alkaline earth) metal halide (M"'X ₂ , X=F, Cl, Br, I, or a mixture thereof) React with the alkali metal tin composition to form an alkali metal (alkaline earth/pseudo-alkaline earth) metal tin composition, wherein the alkaline earth/pseudo-alkaline earth metal is beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, or other combination.

In yet another aspect, the present invention relates to a method for synthesizing a monoalkyl tin compound, wherein the method includes making a primary halide hydrocarbyl compound (RX, where X is a halide atom) and an organometallic The organometallic composition includes a SnL ₃ moiety combined with a metal cation M, wherein M is an alkali metal, an alkaline earth metal, and/or a pseudoalkaline earth metal (Zn, Cd, or Hg), and L is an alkali metal tin that produces The amine ligand of a triamine compound, or the acetylide ligand producing an alkali metal tin triacetylide, correspondingly forms a monoalkyltin triamine (RSn(NR' ₂ ) ₃ ) or a monoalkyltin triacetylide ( RSn(C≡CL ^s ) ₃ ), wherein the monohydrocarbyl ligand (R) has 1 to 31 carbon atoms and optionally an unsaturated carbon-carbon bond, an optional aromatic group, and an optional The hydrocarbon group of the heteroatom, L ^s is SiR" ₃ or R', the three R" are independently H or R', and R' is independently having 1 to 31 carbon atoms and unsaturated carbon-carbon bonds as needed, Optionally aromatic groups, and optionally heteroatom hydrocarbon groups to form an alkali metal tin composition.

In another aspect, the invention relates to compounds represented by the formula RSn(C≡CSiR' ₃ ) ₃ , wherein R' and R independently have 1 to 31 carbon atoms and optionally unsaturated carbon-carbon bonds, optional aromatic groups, and optionally heteroatom hydrocarbon groups.

Furthermore, the present invention relates to halogenated alkyltin compounds represented by the formula R'R" _ACSnZ3 , wherein A is a halogen atom (F, Cl, Br, or I) or an aromatic ring having at least one halogen substituent , wherein R' and R" are independently H, halogen, or a hydrocarbon group having 1 to 15 carbon atoms and optionally unsaturated carbon-carbon bonds, optional aromatic groups, and optional heteroatoms, and Z is L, where L is a hydrolyzable ligand, or O _x (OH) _3-x , 0<x<3.

Furthermore, the present invention relates to an alkyl tin compound represented by the formula R'R"(R'"O) _CSnZ3 , wherein R', R" and R'" are independently hydrogen or have 1 to 15 carbon atoms and optionally An unsaturated carbon-carbon bond, an optional aromatic group, and an optional hydrocarbon group of a heteroatom, and Z is L, where L is a hydrolyzable ligand, or O _x (OH) _3-x , 0＜x＜3.

In some embodiments, the invention relates to alkyltin compounds represented by the formula R'R"(N≡C) _CSnZ3 , wherein R' and R" are independently hydrogen or have 1 to 15 carbon atoms and optionally A saturated carbon-carbon bond, an optional aromatic group, and an optional hydrocarbon group of a heteroatom, and Z is L, where L is a hydrolyzable ligand, or O _x (OH) _3-x , 0<x<3.

Describes a more general and efficient technique for the synthesis of monoalkyl tin compounds, based on reactions involving organic alkali metal compounds, stannous halides (SnX ₂ , X is a halide), organic halides, which are used for The R group for the ligand is donated via a (sp ³ ) carbon-tin bond to tin, optionally another metal compound, and an amine or acetylide, which serves to combine the three hydrolyzable ligands Contribute to tin (NR' ₂ or -C≡CR'). This improved synthesis is based on the putative formation of alkali metal (and/or alkaline earth metal or pseudo-alkaline earth metal, as described below) tin compositions as intermediates in the synthesis of monoalkyl tin compounds, but various metallic tin compositions in other contexts May be useful intermediates. Then, the intermediate metal tin composition reacts with an organic halide to form an R- _SnL3 structure, where R forms a C-Sn bond and L represents a hydrolyzable ligand. Metallic tin compounds have been found to be stable and characterizable in solution, but their separation has so far remained elusive. These metal tin compositions provide convenient precursors for the formation of carbon-tin bonds by replacing metals (alkali metals and/or alkaline earth metals and/or pseudo-alkaline earth metals), have good yields, and are compatible with a variety of organic ligands. There is good specificity, which may be due to the energetics of the reaction. These synthetic methods can then be extended to the synthesis of organotin trialkoxides (triorganoxides) from triamines or triacetylides by substitution of hydrolyzable ligands, or to hydrolysis of ligands And synthesize oxygen/hydroxide compounds. Single organotin compounds, ie compounds with C-Sn bonds that are stable to hydrolysis, can be synthesized directly and produce very low poly-organic contamination, and have been found to be more suitable as radiation-sensitive compositions for patterning applications. Although single organotin triamines can be used directly as precursors for radiation patternable compositions, trialkoxides have been found to be particularly useful precursors for solution or vapor deposition of radiation patternable coatings. Synthetic techniques facilitate the introduction of heteroatom-substituted organic ligands, such as halogenated and functionalized organic ligands, such as those containing cyano or ether groups, which is possible when using other known synthetic techniques Not feasible. Synthetic techniques have been found to be effective in the efficient formation of a variety of organic ligands, and halogenated ligands, particularly iodinated ligands, with high radiation absorption are described and exemplified. This class of compounds is excellent at providing radiation patternable coatings.

As used herein, and generally consistent with usage in the art, "monoalkyl" is used interchangeably with "monorgano" or "monohydrocarbyl," where the "alkyl" ligand means carbon bonded to tin to form Bonds that are generally not hydrolyzable by contact with water, which would involve sp ³ or sp ² mixed into carbon, and "alkyl" groups can have internal unsaturated bonds and heteroatoms, i.e. atoms other than carbon and hydrogen, which Not involved in bonding with tin. The new synthetic method described herein produces monoalkyltin triamines (trialkylamines) and monoalkyltin triacetylides (trihydrocarbyl acetylide). This synthetic method is suitable for efficient scale-up for commercial production of corresponding cost-effective products. With the improved synthetic methods described herein, it becomes more efficient to employ a greater variety of organic functional groups incorporated into the tin and/or amine or acetylide hydrolyzable ligands. The use of reactive species to form the desired compound involves an endothermic reaction. While not wishing to be bound by theory, it is believed that the reactants selected herein alter the reaction, possibly slowing it down, allowing the heat generated to dissipate and/or reducing the heat generated, thereby allowing the formation of less stable R- Sn bonds and/or provide higher product yields. The alternative terminology set forth in the first sentence of this paragraph applies throughout the specification, but further clarification may be gained by adopting terminology that more directly reflects the range of commonly used ligand species. Therefore, the term hydrocarbyl is used to describe a ligand having an sp ³ or sp ² carbon bonded to tin, but the group does not necessarily have a hydrogen atom. Acetylide ligands with sp carbons bonded to tin form hydrolyzable bonds, so they are easily distinguished.

The use of alkyl metal coordination compounds in high-efficiency radiation-based patterning compositions is described, for example, in Meyers et al. entitled "High-resolution patterning compositions based on organometallic solutions". Solution Based High Resolution Patterning Compositions" in U.S. Patent 9,310,684, which is incorporated herein by reference. Improvements in these organometallic compositions for patterning are described in a paper issued to Meyers et al. titled "Organometallic Solution Based High Resolution Patterning Compositions and Corresponding Methods" Corresponding Methods" and U.S. Patent 10,642,153 issued to Meyers et al. and entitled "Organotin Oxide Hydroxide Patterning Compositions, Precursors, and Patterning" U.S. Patent 10,228,618 (hereinafter referred to as the '618 patent), both of which are incorporated herein by reference.

The composition synthesized herein can be an effective precursor for forming alkyltin oxide-oxyhydrogen compositions, which are beneficial to high-resolution patterning, such as in extreme ultraviolet (EUV), Ultraviolet (ultraviolet; UV), electron beam lithography. The alkyltin precursor composition contains groups that can be hydrolyzed with water or other suitable reagents under appropriate conditions to form a monoalkyltin oxide-hydroxide patterning composition, which, when fully hydrolyzed, can be formed by the formula RSnO _{(1.5-(x ／ 2))} (OH) _x represents, where 0 < x ≤ 3. It may be convenient to perform hydrolysis to form the oxygen-oxyhydrogen composition in situ, such as during deposition and/or after formation of the initial coating. While the triamines and triacetylides described herein can be used under hydrolytic conditions to form radiation-sensitive coatings for patterning, it may be desirable to form additional intermediate hydrocarbyltin trialkoxides (triacetylides) used to form coatings. Hydrocarbyl oxides). This article describes processes for forming alkyltin trialkoxides. Various precursor compounds with hydrolyzable ligands are generally synthesized from the perspective of transferring the R-ligand to tin through this process.

Regarding precursors with hydrolyzable ligands, representative hydrolysis and condensation reactions that can transform compositions with hydrolyzable Sn-X groups are represented in the following reactions: RSnL ₃ + 3 H ₂ O → RSn(OH) ₃ + 3 HL, RSn(OH) ₃ → RSnO _{x / 2} OH _3-x + (x / 2) H ₂ O. If the hydrolysis product HL is sufficiently volatile, it can be hydrolyzed in situ with water vapor during substrate coating, but the hydrolysis reaction can also be carried out in solution to form an alkyl tin oxide-hydroxide composition. These processing options are further described in the '618 patent. The overall synthetic process to form a radiation-patternable coating involves forming the required R-Sn (C-Sn) bonds with three hydrolyzable ligands, possibly exchanging the hydrolyzable ligands under appropriate conditions, and Maintain this R ligand.

R forms a carbon-tin bond where the carbon bonded to the tin is ^sp3 or ^sp2 mixed, and R may contain heteroatoms that are not carbon or hydrogen. As noted above, for convenience and consistency in the art, R is interchangeably referred to as an alkyl ligand, an organic ligand, or a hydrocarbyl ligand. In some embodiments, alkyl ligands may be desirable for some patterning compositions, where the compound may generally be represented by R ¹ R ² R ³ CSn O _{(2-(z / 2)-(x / 2 ))} (OH) _x , wherein R ¹ , R ² and R ³ are independently hydrogen or an alkyl group having 1 to 10 carbon atoms. Analogously, this representation of the alkyl ligand R applies analogously to other embodiments generally having R ¹ R ² R ³ CSn(L) ₃ , where L corresponds to a hydrolyzable ligand, for example an alkoxylated (hydrocarbyl oxide), acetylide or amine moiety. In some embodiments, R ¹ and R ² can form a cyclic alkyl moiety, and R ³ can also be bonded to other groups in the cyclic moiety. Suitable branched alkyl ligands may be, for example, isopropyl (R ¹ and R ² are methyl, and R ³ is hydrogen), tertiary butyl (R ¹ , R ² and R ³ are methyl), Tertiary pentyl (R ¹ and R ² are methyl, and R ³ is -CH ₂ CH ₃ ), secondary butyl (R ¹ is methyl, R ² is -CH ₂ CH ₃ , and R ³ is hydrogen ), neopentyl (R ¹ and R ² are hydrogen, and R ³ is -C(CH ₃ ) ₃ ), cyclohexyl, cyclopentyl, cyclobutyl, and cyclopropyl. Examples of suitable cyclic groups include, for example, 1-adamantyl (-C(CH ₂ ) ₃ (CH) ₃ (CH ₂ ) ₃ or tricyclic (3.3.1.13) bonded to a metal at the tertiary carbon ,7) Decane) and 2-adamantyl (-CH(CH) ₂ (CH ₂ ) ₄ (CH) ₂ (CH ₂ ) or tricycle bonded to the metal at the secondary carbon (3.3.1.13, 7) Decane). In other embodiments, the hydrocarbyl group may include an aryl or alkenyl group, such as benzyl, allyl, or alkynyl. In other embodiments, the hydrocarbyl ligand R may include any group consisting solely of C and H and containing 1 to 31 carbon atoms. In summary, some examples of suitable alkyl groups bonded to tin include, for example, linear or branched alkyl (isopropyl ((CH ₃ ) ₂ CH-), tertiary butyl ((CH ₃ ) ₃ C-)), methyl (CH ₃ -), n-butyl (CH ₃ CH ₂ CH ₂ CH ₂ -)), cycloalkyl (cyclopropyl, cyclobutyl, cyclopentyl), alkenyl (ene group, aryl, allyl), or alkynyl, or a combination thereof. In further embodiments, suitable R groups may include hydrocarbyl groups substituted with heteroatom functional groups, including cyano groups, thio groups, silyl groups (and germanium analogs), ether groups, and ketone groups. group, ester group, or halogenated group or a combination thereof. As is conventional in the art, a hydrocarbyl group may be referred to as an alkyl group, even though the group may have unsaturated bonds, aryl groups, heteroatoms, and the like. R with a halogen atom is based on the examples below and is explained in more detail for specific structures. R groups bearing cyano or ether groups are also exemplified below. R groups with silane moieties are described in co-pending provisional application 63 entitled "Organotin Patterning Materials: Compositions and Methods" issued to Jilek et al. /210,769, which application is incorporated herein by reference. R groups with deuterated moieties are described in co-pending U.S. Provisional Patent Application No. 63/215,720 entitled "Deuterated Organotin Compounds" issued to Ilek et al., which application is incorporated by reference incorporated herein.

The precursor composition can be used to form organotin oxy/hydrogen coating compositions that integrate into common oxygen/hydrogen networks. The precursor composition may comprise one or more soluble organotin oxygen/hydroxide compounds, or corresponding compounds having hydrolyzable ligands that upon hydrolysis and/or condensation form oxygen and/or hydroxyl ligands. For precursor compositions with multiple compounds, the compounds may have different organic ligands with metal-carbon bonds, as well as the same or different hydrolyzable ligands. Accordingly, the precursor composition for forming the radiation-sensitive coating may generally comprise solutions of one or more compounds represented by _RSnL3 and mixtures thereof, wherein R is a hydrocarbon group having 1 to 31 carbon atoms, as described above, and L is A ligand with a hydrolyzable ML bond. For the compositions described herein, dialkylamines and alkyl acetylides ( ^-C≡CR0 ) are examples of hydrolyzable ligands. Dialkylamines and alkyl acetylides can be used as ligands, which can be readily substituted and/or reacted to prepare other organotin compositions, such as organotin carboxylates, organotin alkoxides , organotin oxide hydroxide, etc., which can facilitate further processing. Organotin carboxylates can be readily formed by reaction with carboxylic acids. The preparation of organotin alkoxides is illustrated in the examples below, and the formation of organotin oxyhydroxides is summarized below. Organotin alkoxides contain an alkoxy ligand (-OR ⁰ ), where the R ⁰ group can be one of the same moieties described above for R, such that they can have heteroatoms as well as unsaturated carbon -Carbon bonds. In particular, the organotin trialkoxide composition may be represented by the formula RSn(OR ⁰ ) ₃ . Additionally, the organotin trialkylamine composition may be represented by the formula RSn(NR ^a R ^b ) ₃ , wherein the R ^a and R ^b groups may independently be one of the same moieties as described above for R, and The alkyltin trialkyl acetylide can be represented by the formula RSn(C≡CR ⁰ ) ₃ . Like the R ligands, the hydrolyzable ligands refer to alkylamines or alkyl acetylides, which are likewise known in the art to be not limited to alkyl groups in the strict sense of organic chemistry, but can Equivalently stated as organic or hydrocarbyl groups. But for such ligands the term can quickly become more difficult to understand, so for hydrolyzable ligands the alkyl group remains the same, it is understood that this expression should be understood broadly This is a common expression in the art and exemplifies silyl derivatives among hydrolyzable ligands. In some embodiments, R ^a , R ^b , and R ⁰ can independently be linear or branched alkyl (-C _n H _2n+1 , n ranges from 1 to 5).

Monohydrocarbyl tin compositions with hydrolyzable ligands may generally be represented by the _formula RSn(L), where R is as defined above in the context of formation of a carbon-tin bond by sp ^{or sp} carbon, and may be considered The extensive discussion of R above is repeated here in full detail. Regarding hydrolyzable ligands, L can be -OR', NR' ₂ , or -C≡CR'. In general, R' may be any of the same substances as set forth above for R, having as R a sp ³ or sp ² carbon bonded to an adjacent atom, and in particular including unsaturated carbon-carbon bonds if desired , aromatic parts and heteroatoms. Specific examples of silicon heteroatoms are as follows. As with R, the term "alkyl" or "alk", as in "alkoxy", is not meant to be restricted to saturated hydrocarbons containing no heteroatoms, so alternatively it may be called It is a hydrocarbon group or an organic group. In some embodiments, R' may contain ≤10 carbon atoms, and may be, for example, methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, isobutyl, or tertiary pentyl. base. The R groups may be straight chain, branched (ie, secondary or tertiary at the metal-bonded carbon atom), or cyclic. Implementations in which R′ includes silicon atoms will be further described and illustrated below. This article describes various synthetic implementations based on the following general concept: First, an intermediate mixture represented by the formula MSnL ₃ is synthesized, where M is one or more (+1) or (+2) metal ions, and L is a hydrolyzable complex. radicals, especially dialkylamines or alkyl acetylides. Generally, the intermediate is formed at a concentration of about 0.005 M to about 2 M based on the tin content, in further embodiments about 0.01 M to about 1.75 M, and in other embodiments about 1.5 M to about 0.025M. One of ordinary skill in the art will recognize that other concentration ranges within these explicit ranges are contemplated and fall within the scope of this disclosure. This intermediate reacts with RX (where X is a halogen atom) to form RSnL ₃ , which can be further used as desired. In some implementations, M may be Li. In other embodiments, M can be another alkali metal, such as Na, K, Rb, or Cs. In some embodiments, in addition to alkali metals, M may further include alkaline earth metals, such as Mg, Ca, Sr, or Ba. In further embodiments, in addition to alkali metals, M may further include pseudo-alkaline earth metal ions, such as Zn, Cd, or Hg. In some embodiments, M can be a mixture of any of the aforementioned alkali metals, alkaline earth metals, or pseudo-alkaline earth metals. Appropriate selection of M can be driven by thermodynamic and/or kinetic factors, such as the electronegativity difference between M and Sn, which allows the desired alkylation (i.e., Sn-C bond formation) reaction to occur in suitable yields and purity. Other factors that influence the selection of an appropriate M may be physical considerations, such as the hazards posed by the reactants/products (e.g., pyrophoricity, toxicity) and the physical properties of the reactants/products. In any case, it has been found that, in some cases, by using alternative alkali metal ions instead of or in addition to lithium, or by introducing alkaline earths or pseudo-alkaline earths in addition to lithium or other alkali metal ions ions, better yields and purer products can be obtained. Intermediate systems are stable (e.g., do not form precipitates), but due to their reactivity and the resulting difficulty in isolating them, the structures of the intermediates are inferred from available measurements and a review of reasonable alternatives. Therefore, the idealized formula _MSnL3 can be more accurately understood as a complex mixture of intermediates, where M can include one or more metals as described above.

While not wishing to be bound by theory, it is believed that the appropriate choice of M will be affected by the reactivity of the alkylation reaction between the nucleophile _MSnL3 intermediate and the electrophile RX. For more reactive R groups, such as those with low C-Sn bond dissociation energy and/or with high electrophilicity, the energy release from the alkylation reaction is thought to contribute to the dissociation of the Sn-C bond. , leading to poor product yields. Therefore, to reduce the energy released when electrophilic alkyl halides react with nucleophilic MSnL _{intermediates} , it may be desirable for M to include a more electronegative (i.e., less electropositive) metal. Conversely, for less reactive R groups, it may be desirable to select a less electronegative (i.e., more electropositive) metal to increase the yield of the desired RSn bond.

The synthesis method utilizes tin (II) halide (SnX ₂ , such as SnCl ₂ ), secondary amine or acetylide, alkyl metal (MR") and alkyl halide (RX), where R" and R are organic groups, M is an alkali metal (Li, Na, K, Rb, and/or Cs), and X is a halide. The secondary amine can be represented by the formula HNR' ₂ , and the acetylide is represented by R'C≡CH, where R' is an organic group, that is, a hydrocarbon group. For embodiments where M is a non-lithium alkali metal, it may be convenient and more efficient to introduce the alkali metal as MOR ⁰ so that M is incorporated into the alkali metal-tin intermediate. It has not been determined whether LiR "converts to MR" since M can be introduced in a lower stoichiometric amount corresponding to the tinmol amount, rather than the stoichiometric amount of the hydrolyzable ligand. However, the introduction of non-lithium alkali metals can lead to a more efficient overall reaction and improved yields, even though such substitutions may increase reaction complexity and add additional reactants. The intermediates in the synthesis are considered to be MSnL ₃ compositions, where L is -NR' ₂ or -C≡CR'. This alkali metal tin compound can also serve as a useful intermediate for the synthesis of other compounds.

In addition to alkali metals (generally lithium) and optionally non-lithium alkali metals, alkaline earth metal ions (Be, Mg, Ca, Sr, Ba) or pseudo-alkaline earth metal ions (Zn, Cd, Hg) or Mixtures thereof, which for some reactions may help to form products with higher yields and/or higher purity. These +2 metal ions can be introduced as halide salts _MX2 , where X is a halide. It is known that alkaline earth metals (such as magnesium) form equilibrium mixtures of compositions with nucleophilic ligands (including alkyl ligands) in, for example, Grignard reagents. If mixed with a lithium compound bound to a nucleophilic ligand, the alkaline earth metal is expected to form an equilibrium composition with the lithium composition. Pseudo-alkaline earth metals refer to metals in Group 12 of the periodic table of elements (zinc, cadmium, mercury), which exhibit similar chemical properties to the alkaline earth metals in Group 2. Zinc is exemplified below in the synthesis reaction. Compositions formed in solution are conceivable, such as Q(Sn(L ₃ ) ₂ and Li(Q(Sn(L ₃ ) ₃ ), where Q is an alkaline earth metal or a pseudoalkaline earth metal, but the precise combination is not directly assessed species, and relatively complex equilibria may exist. While not wishing to be bound by theory, the introduction of alkaline earth metals and/or pseudo-alkaline earth metals promotes the subsequent formation of tin-carbon bonds by improving reaction pathways and/or intermediates, such that The energy released during the reaction promotes Sn-C bond formation. Alkaline earth metals or pseudo-alkaline earth metals may or may not be added in stoichiometric amounts but can be selected to provide the desired nucleophilicity of the resulting MSnL ₃ intermediate.

Monoalkyltin compositions are typically prepared from monoalkyltin trichloride produced by a redistribution reaction of the following type R ₄ Sn + 3 SnX ₄ → 4 RSnX ₃ R ₂ SnX ₂ + SnX ₄ → 2 RSnX ₃ where R is an alkyl base, and X is a halide, usually a chloride. Langer et al. reported the formation of CH ₃ SnCl ₃ by a redistribution reaction involving (CH ₃ ) ₂ SnCl ₂ and SnCl ₄ in hot dimethylsulfoxide (DMSO). (Tetrahedron Letters, 1967, 1, 43-47; U.S. Patent No. 3,454,610, 1969, both of which are incorporated herein by reference). DMSO forms an adduct with the monoalkyl tin product, which facilitates product isolation and purification.

Catalysts can be used to produce monoalkyl derivatives that would otherwise be difficult or impossible to prepare. The use of phosphorus-halogen compounds in the form of mixtures of phosphorus pentoxide and hydrochloric acid as catalysts is described, for example, in Neumann et al. under the title "Process for the production of alkyltin trihalides"trihalides)", which is incorporated herein by reference. Redistribution of dialkyltin dihalides or tetraalkyltin compositions using tin tetrahalides can also be catalyzed by quaternary ammonium salts at temperatures above 150°C (TG Kugele and DH Parker) DH Parker, U.S. Patent 3,867,198, "Catalyzed redistribution of alkyltin halides", incorporated herein by reference). SnF ₂ has been discovered to catalyze the redistribution reaction (Buschhoff and Neumann), U.S. Patent 4,604,475, "Method for making organotin halides", incorporated herein by reference middle). Thoonen et al. describe the use of transition metal catalyzed redistribution reactions in U.S. Patent 6,768,017 titled "Process for the production of monoalkyl tin trihalides", which patent is incorporated by reference. incorporated herein.

Boele et al. describe olefins, Tin dihalide and hydrogen halide are reacted in the presence of a transition metal catalyst to produce monoalkyltin trihalide, which patent is incorporated herein by reference. Deelman et al. describe the purification of monoalkyltin trichloride and its purification by This was converted into a derivative composition by replacing the chloride with thioglycolate, which patent is incorporated herein by reference.

While several methods are available for preparing monoalkyltin compositions, their applicability is often limited to specific alkyl groups due to practical issues. In addition, the reported reactions may also produce low product yields and multiple mono- and polyalkyl products that are involved in subsequent purification steps to isolate the desired compounds. Residual catalyst in the product may also harm applications requiring trace metals at very low concentrations.

Edelson et al. describe improved methods for the synthesis of monoalkyltin triamines and monoalkyltin trialkoxides in published U.S. patent application 2019/0315781A1, which is titled "Methods with Low Polyalkyl Contamination" "Monoalkyl Tin Compounds with Low Polyalkyl Contamination, Their Compositions and Methods" is incorporated herein by reference. Triamines are prepared by substitution reactions between alkyl zinc or alkyl magnesium reagents and tin tetramines. The product triamine is then purified by fractional distillation to remove polyalkyl impurities. The triamine can then be converted to the trialkoxide by reacting the amine with a stoichiometric amount of alcohol. This work involves generating small amounts of polyalkyl impurities from the initial reaction, but using fractionation to further reduce impurity levels.

Methods for preparing monoalkyltin triamines have previously used lithium reagents to convert tin tetramines to the desired triamines. For example, tertiary butyl tris(diethylamino)tin (t-BuSn(NEt ₂ ) ₃ ) can be synthesized using lithium reagents according to the method in the following literature: Hänssgen, D. ); Puff, H.; Beckerman, N., J. Organomet. Chem. 1985, 293, 191, incorporated herein by reference. However, these methods using lithium reagents can produce mixtures of monoalkyltin products and dialkyltin products. The reported method for preparing monoalkyltin triamines containing secondary alkyl groups produces a mixture rich in mono-, di-, and trialkyltin products.

The methods described herein focus on the synthesis of monoalkyltin triamines and monoalkyltin triacetylides with low polyalkyl concentrations prior to distillation. These methods can also be used to synthesize monoalkyltin products containing hydrocarbyl groups that cannot be readily prepared in pure form by other methods known in the art. In this synthesis reaction, the hydrocarbyl ligand is generated from the organic halide reactant. Organohalide reactants can be readily used in a variety of compounds to provide ligands. Although other synthetic techniques can generally be used for the synthesis of various hydrocarbyl ligands, there may be practical limitations on the composition of the reactants to introduce the ligands, as well as the selection of yields, reaction times, and appropriate solvents, and there may be other potential practical limitations. The synthesis of alkali metal tin compounds provides a useful intermediate that may also be useful in other situations.

Regarding designing improved EUV patterning compositions, it may be advantageous to tailor the hydrocarbyl ligands to include atoms with high EUV absorption (eg, iodine) to increase the efficiency of the patterning process. In the processes _described herein, the organic halide reactant may be an iodinated organic halide represented by the formula R _I radical, alkynyl, aryl), in which at least one hydrogen atom is replaced by an iodine atom. X is a halide, including iodide, chloride, and bromide. In some embodiments, other halide groups can be similarly introduced as replacements for the iodide groups, so R _I can also be considered to have other halides instead of iodine. Generally speaking, the reactants have multiple halogen atoms because one halogen atom is replaced by nucleophilic substitution to form a tin-carbon bond, while the other halogen atoms remain in the halogenated ligand. When halides are present in unequal amounts, the carbon atoms bonded directly to the halide will have different electrophilicities depending on the identity of the halide, so by ensuring that the appropriate halide is on the desired carbon , in this way it is possible to direct the reaction to the correct product. Generally speaking, for smaller halides, carbon is more electrophilic, but there are always other considerations. In general, this reaction allows for the highly selective addition of more electrophilic carbons.

Depending on the situation, R _I may also have other heteroatom substitutions, such as N, O, P, S, or other halogen atoms. Non-limiting examples of iodinated organohalide reactants include 2,2-diiodopropane and 3-iodobenzyl bromide. Other conceivable iodinated organohalide reactants have 2 or 3 or more iodine atoms in the hydrocarbyl group. Fully iodinated aryl halides are also contemplated. The iodinated organic halide reactant can be used to synthesize monoalkyltin triamine and monoalkyltin acetylide products containing iodinated hydrocarbyl ligands. The iodinated alkyltin trialkoxides may be formed further as described herein for non-iodinated alkyltin trialkoxides. For the purposes of this disclosure, reactions involving RX or _RSnL compounds are considered interchangeable with _RIX or _{RI SnL} compounds. In some desirable embodiments, the halogenated ligand has a structure represented by the formula R ¹ R ² XC-, wherein R ¹ and R ² are independently H or any other organic moiety consistent with the broad definition of R above, provided that That is, neither R nor R' is H, and X is a halide, that is, F, Cl, Br, or I. Therefore, in these compounds, the halogen atoms are bonded directly to the carbon forming the tin bond. After the synthesis is completed, the product compound with optional hydrolysis and/or condensation can be represented by the formula R ¹ R ² XCSnZ ₃ , where Z is L, where L is a hydrolyzable ligand, or O _x (OH) _3-x ,0<x<3. In other desirable embodiments, the halogenated ligand is represented by the formula AR ¹ R ² C-, where A is an aromatic ring with at least one halogen substituent, and R ¹ and R ² are independently H or a generalized version of the above R Any other organic part that is consistently defined. A can be C ₆ H ₄ X, C ₆ H ₃ X ₂ , C ₆ X ₅ , or any other reasonable aromatic ring, where After the synthesis is completed, the product compound with optional hydrolysis and/or condensation can be represented by the formula AR ¹ R ² CSnZ ₃ , and Z is L, where L is a hydrolyzable ligand or O _x (OH) _3-x , 0＜x＜3. In particular, iodine has large EUV absorption. Although other halogens have less significant EUV absorption, it is still advantageous for them to replace hydrogen since hydrogen has less significant EUV absorption.

Exemplary precursor compounds also include R groups bearing cyano (also known as nitrile) or ether groups. The cyano compound may have the formula R'R"(N≡C)CSnZ ₃ , wherein R' and R" independently have 1 to 15 carbon atoms and optionally unsaturated carbon-carbon bonds, optionally aromatic groups group, and optionally a hydrocarbon group of heteroatoms, and Z is L, wherein L is a hydrolyzable ligand, or O _x (OH) _3-x , 0<x<3. In some embodiments, R' and R" are the same and R' is a linear or branched alkyl group (-C _n H _2n+1 , n is 1 to 5). The compound with an ether group can have the formula R'R"(R'"O)CSnL ₃ , wherein R', R'' and R'" are independently hydrogen or have 1 to 15 carbon atoms and optional unsaturated carbon-carbon bonds, optional aromatic groups group, and optionally a hydrocarbon group of heteroatoms, and Z is L, where L is a hydrolyzable ligand, or O _x (OH) _3-x , 0＜x＜3

Although the overall synthesis can be thought of as two overall steps, more generally the synthesis can be thought of as a multi-step process, but the number of steps may be subjective since the intermediates are generally not isolated and purified. While not wishing to be bound by theory, conceptually it is useful to consider that the overall synthesis process consists of two steps, the first of which involves the formation of a metal-tin bond with three amine/acetylide ligands (the metal is a base). Metals and/or alkaline earth metals/pseudo-alkaline earth metals) four-coordinated tin can have both ionic and covalent characteristics, but this concept is not limited by structural theory. In a second step, the metal-tin interaction is replaced by a hydrocarbyl ligand connected to the tin involving an sp ³ or sp ² carbon-tin bond. The overall reaction involves the oxidation of tin(II) to tin(IV) and the corresponding exchange of two halide ligands into three amine/acetylide ligands and a carbon-tin bond. The first step in forming the metallic tin triamine/acetylide can generally be conceptually divided into multiple steps depending on the specific feedstock.

As illustrated, monoalkyltin triamines and monoalkyltin triacetylides can be prepared by the following overall reaction: 3 HNR' ₂ + 3 MR" (+ M'Z) + SnX ₂ + RX → RSn(NR' ₂ ) ₃ + by-product, or 3 R'CCH + 3 MR" (+ M'Z) + SnX ₂ + RX→ RSn(CCR') ₃ + by-product. (1) In these reactions, M is generally lithium, but lithium can be replaced by other alkali metals, that is, sodium, potassium, rubidium, and cesium. _M'Z in parentheses represents the optional reactant M"OR" or M'" Metal ions, provided as halides, where X is a halide ion. From a practical point of view of some target products, if alkali metal alkoxide (MOR ⁰ ) is added in the first step of the reaction, the reaction will obtain better yield and reaction rate. Furthermore, for such processing, the desired reactants can be obtained more easily. However, for some organic ligands, better yields can be obtained by introducing non-lithium alkali metal compounds. Thus, other exemplary embodiments involving potassium have the following overall reaction: 3 HNR' ₂ + 3 LiR" + KOR ⁰ + SnX ₂ + RX → RSn(NR' ₂ ) ₃ + by-product, or 3 R'CCH + 3 LiR" + KOR ⁰ + SnX ₂ + RX → RSn(CCR') ₃ + by-product, (2) In the reactions represented by these reaction formulas, potassium (K) can be replaced by other non-lithium alkali metal ions substitute. Example 7 illustrates the synthesis of alkyltin triamine iodide represented by the formula (CH ₃ ) ₂ ICSn(N(CH ₂ ) ₂ ) ₃ by reaction according to reaction (2). The synthesis includes both n-butyllithium and tertiary potassium butoxide as well as iodinated alkyl halides. Example 8 illustrates the synthesis of aryltin triacetylide iodide represented by (C ₆ H ₅ I)CH ₂ Sn (CCSi(CH ₃ ) ₃ ) by reaction according to reaction (2). The synthesis involves both n-butyllithium and tertiary potassium butoxide as well as an iodinated aryl halide. In reactions (1) and (2), X is a halide, and R' is generally a hydrocarbon group of ≤10 carbon atoms. R" is incorporated into a by-product, typically HR", so its identity is generally of no particular limitation or importance, and can generally be based on availability, low cost, ease of removal of by-products, and good reactivity And choose. The R' group provides a substituent for the corresponding ligand of the product composition. In reaction formula (2), potassium can be introduced in a stoichiometric amount relative to the tin used to form the potassium-tin composition, rather than in a stoichiometric amount used to introduce the amine ligand. This is the reason why in this reaction In the case of lithium. In additional or alternative embodiments, KOR ⁰ may be replaced or supplemented by M"X ₂ (eg, ZnCl ₂ ), where M" is an alkaline earth metal ion or a pseudoalkaline earth metal ion.

In some embodiments, it may be beneficial to perform the above reaction in the presence of a suitable additive such as tris(2-aminoethyl)amine (TREN), such as Edson ) and others in published U.S. patent application 2019/0315781 (hereinafter referred to as the '781 application), the application is titled "Monoalkyltin compounds with low polyalkyl contamination, compositions and methods thereof (Monoalykyl Tin Compounds with Low Polyalkyl Contamination, Their Compositions and Methods)", incorporated herein by reference. This kind of additive can improve product purity, reduce the activation energy of reaction steps, catalyze reaction steps, etc. The above reaction can be carried out in a suitable solvent, which is selected based on various properties such as suitable reactants and products, such as solvation, toxicity, and flammability. After preparing the improved photosensitive composition, the composition can be further purified if necessary. In some implementations, as described in the '781 application, fractionation methods may be effectively used.

The RX organohalide was chosen to provide the required organic ligands for the single organotin product. The wide availability of RX compounds as reactants and the broad reactivity of these compounds in corresponding reactions enable the introduction of various organic ligands into single organotin products with practical yields and reasonable reaction times. The products illustrated demonstrate their versatility to a certain extent.

As explained further below, the overall reaction can be considered to be the result of two or more consecutive reactions, but isolation or purification of intermediates is generally not performed. The first reaction involves the synthesis of an alkali metal amine or alkali metal acetylide, such as lithium amine or lithium acetylide. Although lithium amine and lithium acetylide are well-known compounds, and some are commercially available in some form, these compounds are highly reactive and pyrophoric, so in situ synthesis of these compounds as part of the overall reaction is Convenient and beneficial. Regarding non-lithium alkali metal amines or non-lithium alkali metal acetylides, these compounds can be synthesized analogously. However, in some embodiments, the non-lithium alkali metal may be introduced in a stoichiometric amount similar to tin, rather than three times the amount corresponding to the amine/acetylide ligand. Non-lithium metal ions may be more conveniently provided in the form of alkali metal alkoxide compounds and/or alkaline earth/pseudo-alkaline earth metal dichalcogenides, where alkali metal alkoxide compounds are more readily available than other alkali metal precursor compounds. Tin dihalides, such as tin dichloride, react with alkali metal amines to form alkali metal tin triamine or alkali metal tin triacetylide.

At present, the separation of alkali metal tin triamine or alkali metal tin triacetylide has not been realized. Improved synthetic techniques do not depend on the exact identities of intermediates, and the general discussion herein focuses on the total starting materials and final products that can be isolated and characterized. However, the identities of the putative intermediates are based on strong assumptions inferred from the substances present. Metal ions are not expected to be well solvated in the particular solvent used. However, the composition remained in solution and therefore no large cluster formation and gelation was observed. While not wishing to be bound by theory, organometallic reagents such as alkyllithiums, alkylmagnesiums (Grenya reagents), and potassium tertiary butoxides are known to form clusters with metal-metal bonds, such as tetramers , hexamers and cubanes, it is therefore reasonable to form similar substances in solution in the form of complex equilibrium mixtures of possible complex equilibrium mixtures that have been difficult to characterize so far. Thus, the relative stabilities of known substances suggest what intermediate species may be present, but precise structural characterization is not required to understand their basic chemical involvement in the reaction. Reactivity of a substance is consistent with the inability to remove the solvent to separate the substance.

Although the overall reaction is given above, the reactions are carried out in multiple steps. Since one of the reactants is a tin dihalide, such as tin dichloride, solvent selection considerations include appropriate solubility of the tin dihalide. Other initial reactants such as dialkyl amines and monoalkyl lithiums (or generally monoalkyl alkali metals) are soluble in different solvents. The reaction is generally carried out in a dry organic solvent in an oxygen-free or oxygen-deficient atmosphere, such as a nitrogen purged atmosphere. Solvents can be selected to produce dissolution of the various components. Due to the interaction of the solvent with the metal ions, the selection of the solvent can be based at least in part on the reaction rate in the selected solvent, which can be evaluated empirically. If different solvents are chosen, they are generally miscible. Aprotic polar solvents are generally useful, such as ethers (eg, dimethyl ether, diethyl ether), tetrahydrofuran (THF), acetone, and mixtures thereof. Solvents should generally be selected to be inert toward the reactants, intermediates, and products. If multiple solvents are used, for example to introduce different reactants, the solvents should generally be miscible with each other. The first reaction can be considered to be the synthesis of MSnL ₃ intermediate, where L is dialkylamine (dialkylamine) or alkyl acetylide (alkyl acetylide), but the specific structure has not been verified. Looking at the reactants and reaction conditions, the evidence does show that a tin-ligand bond is formed, so the presence of the SnL ₃ moiety seems possible, and it seems possible that the metal cation binds to the tin moiety to stabilize it, but the specific structure may Exists in complex balanced mixtures. If desired, this first reaction can be considered as two separate reactions, where the first sub-reaction involves the formation of the metal ligand composition (ML), and the subsequent sub-reaction involves _SnCl2 or other tin dihalides. As specified, M can be an alkali metal, an alkaline earth metal, and/or a pseudo-alkaline earth metal. Generally speaking, for the first reaction, the solution is cooled, usually below 10°C, and in some embodiments to 0°C, which is a convenient temperature for the use of an ice bath, but for non-aqueous solutions, There is nothing special about the temperature. Cooling allows control of the desired reaction while maintaining a reasonable reaction rate. The first sub-reaction can be carried out for a feasible period of time without particular restrictions. The first sub-reaction may be allowed to last for at least about 30 seconds, in other embodiments at least about 2 minutes, in some embodiments from 1 minute to about 5 hours, and in some embodiments from about 2 minutes to about 3 hours. In some embodiments, the two sub-reactions can be combined and performed essentially as a single reaction, effectively this is zero time for the first sub-reaction, or a short time for the first sub-reaction. If non-lithium alkali metal alkoxides and/or alkaline earth metal (or pseudo-alkaline earth metal) dihalides are introduced as reactants, then conceptually the compounds can be added as part of the first subreaction or the second subreaction, Or potentially added in a third sub-reaction between the first sub-reaction and the second sub-reaction. One of ordinary skill in the art will recognize that other time and temperature ranges within the explicit ranges set forth above are contemplated and fall within the scope of the present disclosure.

Generally speaking, the alkyllithium reactant and the amine/acetylene reactant are in approximately stoichiometric amounts, although a small to moderate excess of the amine/acetylene reactant is typically used, for example, about 1 molar percent (mol%) to Approximately 50 mole % of amine/acetylene reactant. If non-lithium alkyl alkali metal compounds are used, similar stoichiometric amounts of ligand precursors (dialkylamines or alkyl acetylenes) can be used. Generally speaking, a ML composition with a ratio of 3:1 relative to the molar amount of Sn is desired, adding three ligands for each tin. If a non-lithium metal alkoxide alkali metal compound is used with an alkyl lithium, the alkyl lithium can have an amount based on molar equivalents of the amine/acetylene reactant, and the non-alkali metal compound can have an amount equal to the tin compound to be added. Molar amounts, but larger amounts of metal (alkali or alkaline earth metals or pseudo-alkaline earth metals) may be used if desired, as long as additional amounts of ML are not formed. For corresponding embodiments, tin reactants may be added in approximate molar equivalents (1:3) of reactants contributing ML ligands to form three ligand tin bonds per tin atom. Low levels of contaminant tin products with 1, 2 or 4 ligands demonstrate the effectiveness of controlling the molar ratio of tin to ML reactants. The metal concentration in the reactant solution is generally about 0.025 M to about 2 M, and in further embodiments, about 0.5 M to about 1.5 M. One of ordinary skill in the art will recognize that concentration ranges and allowable stoichiometric ratios within the above-mentioned explicit ranges are contemplated and fall within the scope of the present disclosure.

The second reaction involves the introduction of carbon-tin bonds and the formation of organic ligands that bind the tin. Carbon-tin bonds conceptually replace metal-tin bonds, where the metals are alkali metals, alkaline earth metals and/or pseudo-alkaline earth metals. The organic ligand bound to tin is produced by reaction with the organic halide RX. Generally, the organic halide is introduced in at least about a stoichiometric amount to form a carbon-tin bond, but an excess of the organic halide can be introduced. In some embodiments, up to a threefold molar excess of the organic halide may be used in the reaction, and in further embodiments, about 1 to about 2 molar equivalents relative to the moles of tin may be used. RX. The solvent may be the same as that used for the first reactant, or may be selected from the same available solvents and mixtures thereof. The product of the first reaction is generally not purified before carrying out the second reaction, but by-products can be removed if convenient. The metal concentration is generally similar to that of the first reaction step, but is usually slightly smaller due to dilution. Considering the exothermic nature of the reaction, the second reaction generally but not necessarily starts at a low temperature, such as about 0°C or more generally about -78.5°C to about 10°C, but in some embodiments, the reactants can be at room temperature. mix. After mixing the reactants for the second reaction, the reaction may be allowed to continue at the same temperature, or the reaction may be allowed to gradually warm to a temperature of about 20°C to about 50°C or room temperature (20 to 24°C). The reaction can proceed for at least about 15 minutes, in some embodiments from about 15 minutes to about 24 hours, and in some embodiments from about 30 minutes to about 15 hours, although longer reaction times can be used if desired. . One of ordinary skill in the art will recognize that other ranges of concentrations, molar ratios, temperatures, and times for the second reaction given above are contemplated and fall within the scope of the present disclosure.

Due to the exothermic nature of the reactions described herein, it may be beneficial to vary various parameters of the synthesis, such as amounts of reactants, reaction temperature, reagent addition times, reaction times, etc. Such considerations are known to those of ordinary skill in the art. A useful analytical technique for analyzing reactions and informing practitioners of appropriate process conditions is reaction calorimetry. Calorimetric data can provide useful thermodynamic variables for a given reaction. Specifically, scale-dependent variables of a desired reaction (eg, enthalpy) can be measured and used to appropriately conduct the reaction at larger scales. In this way, process variables can be appropriately controlled for reactions of different scales. Reaction calorimetric data are included in some examples below. In light of the guidelines given above and the examples below, one of ordinary skill in the art will recognize that the specific parameters for a particular reaction can be adjusted to provide the desired results. Based on these teachings, one with ordinary knowledge can optimize a variety of product compositions using routine experimentation. The illustrated reactions yield good yields and high specificity for product composition.

Once the product is formed, the organotin tris(dialkylamine/alkyl acetylide) can be purified. The purification end depends on the nature of the product, but generally involves separating the desired product from by-products and potentially any unreacted reagents. Purification can generally be accomplished by methods known in the art. Typical purification methods may include filtration, recrystallization, extraction, distillation, combinations thereof, etc. The crude product mixture is typically filtered to remove insoluble contaminants and/or by-products, such as metal halide salts such as LiCl, from the solution containing the desired product. Recrystallization methods can be used to purify solid compounds by heating to form a saturated solution and then cooling. Extraction techniques may include, for example, liquid-liquid extraction, in which two immiscible solvents of different densities are used to separate the desired compounds based on their relative solubilities. Purification may also include removal of any volatile compounds, including solvents, from the product mixture by drying or exposure to vacuum. For products with significant vapor pressure, it may be desirable to purify the product by vacuum distillation or, if necessary, by fractional distillation aimed at obtaining high purity. See published U.S. Patent Application 2020/0241413 to Clark et al., entitled "Monoalkyltin trialkoxides and/or monoalkyltin with low metal contamination and/or particle contamination. Triamines and Corresponding Methods (Monoalkyl Tin Trialkoxides and/or Monoalkyl Tin Triamides With Low Metal Contamination and/or Particulate Contamination and Corresponding Methods)," are incorporated herein by reference. The products may also react to form derivatives, such as organotin trialkoxides, which may be further purified by the techniques described above and other methods known in the art.

The organotin precursor compositions described herein are effective for radiation patterning, especially EUV patterning. The ability to have greater flexibility in ligand selection allows for further improvements in patterning results, as well as the design of ligands that are particularly effective for specific applications. In general, any suitable coating process can be used to deliver the precursor solution to the substrate. Suitable coating methods may include, for example, solution deposition techniques such as spin coating, spray coating, dip coating, knife edge coating, printing such as inkjet printing and screen printing, and the like. Many precursors are also suitable for vapor deposition on substrates, as discussed in the '618 patent cited above. For some R-ligand compositions and/or specific process considerations, vapor deposition can be used to prepare radiation-sensitive coatings.

For patterning compositions used for solution deposition, it may be desirable to convert the product to an organotin trialkoxide. This reaction is generally carried out by reacting with the corresponding alcohol after distillation and purification. May be used with or without additional solvents. To better control the reaction, the reaction can first be cooled, for example to ice bath temperature, and then allowed to warm to room temperature. The product organotin trialkoxides are generally oils that can be purified by distillation. The following examples outline these steps. Forming the coating precursor does not require conversion of the precursor composition to a trialkoxide, but organotin trialkoxides can be convenient precursors for deposition because of the benign volatile products following hydrolysis and coating formation. For example, alcohol.

After preparing the desired organotin precursor, the precursor can be dissolved in a suitable solvent to prepare a precursor solution, such as an organic solvent, such as alcohols, aromatic and aliphatic hydrocarbons, esters, or combinations thereof. In particular, suitable solvents include, for example, aromatic compounds (e.g. xylene, toluene), ethers (e.g. anisole, tetrahydrofuran), esters (propylene glycol monomethyl ether acetate, ethyl acetate, ethyl lactate), alcohols (e.g. 4-methyl-2-pentanol, 1-butanol, methanol, isopropanol, 1-propanol), ketones (such as methyl ethyl ketone), mixtures thereof, etc. In general, the choice of organic solvent will be influenced by solubility parameters, volatility, flammability, toxicity, viscosity, and potential chemical interactions with other process materials. After the components of a solution dissolve and combine, the properties of the substance may change due to partial in-situ hydrolysis, hydration and/or condensation.

The organotin precursor can be dissolved in the solvent at a concentration that provides a tin concentration suitable for forming a coating with a thickness suitable for processing. The concentration of substances in the precursor solution can be selected to obtain the desired physical properties of the solution. Specifically, lower concentrations can generally result in solution properties that are desirable for certain coating methods, such as spin coating, that can achieve thinner coatings using reasonable coating parameters. It may be desirable to use thinner coatings to achieve ultrafine patterning and reduce material costs. In general, the concentration can be chosen to suit the chosen coating method. Coating properties are further explained below. Generally, tin concentrations include from about 0.005 M to about 1.4 M, in further embodiments from about 0.02 M to about 1.2 M, and in additional embodiments from about 0.1 M to about 1.0 M. One of ordinary skill in the art will recognize that other tin concentration ranges within the explicit ranges set forth above are contemplated and fall within the scope of the present disclosure.

In some embodiments, the improved photosensitive precursor composition may be present in a mixed solution with one or more organotin compositions (such as R _n SnX _4-n and its hydrolyzate), wherein R is selected from the group consisting of those described in detail herein and the various parts expressly set out above. These mixed solutions can be adjusted to optimize various performance considerations such as solution stability, coating uniformity and patterning performance. In some embodiments, the improved photosensitive composition may comprise the required components in a mixed solution of at least 1 mol% tin, in a further embodiment the mixed solution is at least 10% molten tin, in a further embodiment In one embodiment, the mixed solution contains at least 20 mol% tin, and in a further embodiment, the mixed solution contains at least 50 mol% tin. Other molar % ranges of improved photosensitive compositions within the specified range of the mixed solution are contemplated and are within the scope of this disclosure.

The organotin compositions described herein may be used as precursors for forming coatings by vapor deposition, generally due to their high vapor pressure. Vapor deposition methods generally include chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), and improved methods thereof. In a typical vapor deposition process, the organotin composition can react with small molecule gas phase reagents, such as H ₂ O, O ₂ , H ₂ O ₂ , O ₃ , CH ₃ OH, HCOOH, CH ₃ COOH, etc., which Used as O source and H source for the production of radiation-sensitive organic tin oxide and oxyhydroxide coatings. Wu et al. describe the vapor deposition of radiation-patternable organic tin coatings in PCT application PCT/US2019/031618, which is titled "Methods for Making EUV-Patternable Hard Masks" EUV Patternable Hard Masks)", incorporated herein by reference. The production of radiation-sensitive organotin coatings is generally achieved by reacting the volatile organotin precursor RSnL ₃ with small gas phase molecules. The reaction may include hydrolysis/condensation of the organotin precursor to hydrolyze the hydrolyzable ligand while leaving the Sn-C bond substantially unchanged.

An overview of representative processes for radiation-based patterning, such as extreme ultraviolet (EUV) lithography processes, in which photoresist materials are deposited or coated as a thin film on a substrate, baked before exposure, and patterned with radiation to create a latent image, After exposure, it is baked and then developed with a liquid (usually an organic solvent) to produce a developed pattern of the photoresist. If desired, fewer steps can be used, and additional steps can be used to remove residue to increase pattern fidelity.

The thickness of the radiation patternable coating may depend on the required manufacturing process. For use in single-patterned EUV lithography, the coating thickness is generally selected to produce patterns with low defectivity and patterning reproducibility. In some embodiments, a suitable coating thickness may be between 0.1 nanometer and 100 nanometers, in further embodiments about 1 nanometer to 50 nanometers, and in further embodiments about 2 nanometers. nanometer to 25 nanometer. One of ordinary skill in the art will understand that other coating thickness ranges are contemplated and fall within the scope of this disclosure.

The coating thickness of a radiation patternable coating prepared by vapor deposition technology can generally be controlled by appropriately selecting the reaction time or cycle number of the process. The thickness of the radiation patternable coating may depend on the required manufacturing process. For use in single-patterned EUV lithography, the coating thickness is generally selected to produce patterns with low defects and pattern reproducibility. In some implementations, a suitable coating thickness may be between 0.1 nanometer and 100 nanometers, in further implementations about 1 nanometer to 50 nanometers, in further implementations about 2 nanometers. meters to 25 nm. One of ordinary skill in the art will understand that other coating thickness ranges are contemplated and fall within the scope of this disclosure.

The substrate generally has a surface on which the coating material can be deposited, and it can include multiple layers, with the surface being associated with the uppermost layer. The substrate is not particularly limited and may include any reasonable material, such as silicon, silicon dioxide, other inorganic materials (such as ceramics), and polymer materials.

After deposition and formation of the radiation patternable coating, further processing can be performed prior to radiation exposure. In some embodiments, the coating can be between 30°C and 300°C, in further embodiments between 50°C and 200°C, and in further embodiments between 80°C and 150°C. Heating time. Heating may occur in some embodiments from about 10 seconds to about 10 minutes, in further embodiments from about 30 seconds to about 5 minutes, and in further embodiments from about 45 seconds to about 2 minutes. Other temperature and heating duration ranges within the explicit ranges above are foreseeable and contemplated.

Patterning of compositions:

Radiation can generally be directed to the substrate being coated via a photomask, or the radiation beam can be controllably scanned across the substrate. Generally speaking, radiation may include electromagnetic radiation, electron beam (beta radiation), or other suitable radiation. Generally speaking, electromagnetic radiation may have a desired wavelength or range of wavelengths, such as visible radiation, ultraviolet radiation, or X-ray radiation. The resolution that can be achieved with a radiation pattern generally depends on the wavelength of the radiation, and higher resolution patterns can generally be achieved with radiation of shorter wavelengths. Therefore, it may be desirable to use ultraviolet light, X-ray radiation, or electron beams to obtain particularly high-resolution patterns.

According to the international standard ISO 21348 (2007), which is incorporated herein by reference, ultraviolet light extends between wavelengths longer than or equal to 100 nanometers and shorter than 400 nanometers. Krypton fluoride laser can be used as a source of 248 nm ultraviolet light. Depending on the accepted criteria, the UV range can be subdivided in several ways, such as extreme ultraviolet (EUV) from 10 nanometers or more to less than 121 nanometers and far-UVC from 122 nanometers or more to less than 200 nanometers. (far ultraviolet; FUV). 193 nanowires from argon fluoride lasers can be used as radiation sources in FUV. 13.5 nm EUV light has been used for lithography, and this light is produced by Xe or Sn plasma sources excited by high-energy lasers or discharge pulses. Soft X-rays can be defined as longer than or equal to 0.1 nanometers to shorter than 10 nanometers.

Based on the design of the coating material, there can be a large contrast in material properties between the irradiated areas with the condensation coating material and the unirradiated areas of the coated material where the Sn-C bonds remain substantially unchanged. For embodiments in which post-irradiation heat treatment is used, the post-irradiation heat treatment may be at about 45°C to about 250°C, in additional embodiments about 50°C to about 190°C, and in further embodiments about It is carried out at a temperature of 60°C to about 175°C. Post-exposure heating can generally be performed for at least about 0.1 minutes, in further embodiments from about 0.5 minutes to about 30 minutes, and in additional embodiments from about 0.75 minutes to about 10 minutes. One of ordinary skill in the art will recognize that other post-irradiation heating temperature and time ranges within the explicit ranges set forth above are contemplated and fall within the scope of the present disclosure. This high contrast in material properties further facilitates the formation of high-resolution lines with smooth edges in the pattern after development, as described below.

For negative imaging, the developer can be an organic solvent, such as the solvent used to form the precursor solution. In general, the choice of developer can be influenced by the solubility parameters of both irradiated and non-irradiated coating materials, as well as developer volatility, flammability, toxicity, viscosity, and potential chemical interactions with other process materials. . In particular, suitable developers include, for example, alcohols (eg, 4-methyl-2-pentanol, 1-butanol, isopropanol, 1-propanol, methanol), ethyl lactate, ethers ( For example, tetrahydrofuran, dioxane, anisole), ketones (pentanone, hexanone, 2-heptanone, octanone), etc. Development may occur from about 5 seconds to about 30 minutes, in further embodiments from about 8 seconds to about 15 minutes, and in additional embodiments from about 10 seconds to about 10 minutes. One of ordinary skill in the art will recognize that other ranges within the explicit scope described above are contemplated and fall within the scope of the present disclosure. In addition to the main developer composition, the developer may contain additional additive compositions to facilitate the development process. Suitable additives may include, for example, viscosity modifiers, solubilizing aids, or other processing aids. If optional additives are present, the developer may contain no more than about 10% by weight of additives, and in further embodiments no more than about 5% by weight of additives. One of ordinary skill in the art will recognize that other additive concentration ranges within the explicit ranges set forth above are contemplated and fall within the scope of the present disclosure.

For weaker developers where the coating has a lower development rate, such as a dilute organic developer or composition, a higher temperature development process can be used to increase the rate of the process. For stronger developers, the temperature of the development process can be lower to reduce the rate and/or control the kinetics of development. Generally speaking, the temperature of development can be adjusted between appropriate values consistent with the volatility of the solvent. Additionally, during development, the developer and dissolved coating material near the developer-coating interface can be dispersed by ultrasound. Any reasonable method may be used to apply the developer to the patterned coating material. For example, the developer can be sprayed onto the patterned coating material. Additionally, spin coating can be used. For automated processing, the paddle method can be used, which involves pouring the developer in a fixed pattern onto the coating material. If desired, spin rinsing and/or drying can be used to complete the development process. Suitable rinsing solutions include, for example, ultrapure water, aqueous tetraalkyl ammonium hydroxide, methanol, ethanol, propanol, and combinations thereof. After the image is developed, the coating material is placed on the substrate as a pattern.

In some embodiments, the solvent-free (dry) development process can be performed by using an appropriate thermal development or plasma development process, such as that described by Tan et al. in U.S. Patent Application No. PCT/US2020/039615 Stated, the application is entitled "Photoresist Development With Halide Chemistries" and is incorporated herein by reference. For organic tin photoresist coatings, dry development can be performed by using halogen-containing plasmas and gases (such as HBr and BCl ₃ ). In some cases, dry development can provide advantages over wet development, such as reduced pattern collapse, reduced scum, and fine control of the developer composition (ie, plasma and/or etching gases).

After the development step is completed, the coating material can be heat treated to further condense the material and further dehydrate, densify, or remove residual developer from the material. Such heat treatment may be particularly desirable for embodiments in which the oxide coating material is incorporated into the final device, but may be particularly desirable for some embodiments in which the coating material is used as a photoresist and ultimately removed. In other words, if it is desired to stabilize the coating material to facilitate further patterning, thermal treatment may be desirable. In particular, baking of the patterned coating material can be performed under conditions where the patterned coating material exhibits a desired level of etch selectivity. In some embodiments, the patterned coating material can be heated to about 100°C to about 600°C, in further embodiments about 175°C to about 500°C, and in additional embodiments about 200°C. to a temperature of approximately 400°C. Heating can be performed for at least about 1 minute, in other embodiments from about 2 minutes to about 1 hour, in further embodiments from about 2.5 minutes to about 25 minutes. Heating can be performed in air, vacuum or an inert gas environment (such as Ar or N ₂ ). One of ordinary skill in the art will recognize that other temperature and time ranges for heat treatment within the explicit ranges set forth above are contemplated and fall within the scope of the present disclosure. Likewise, non-thermal treatments involving blanket UV exposure or exposure to oxidizing plasmas such as _O can be used for similar purposes. Example

The following examples present the synthesis and NMR characterization of monoalkyltin triamine, triacetylide, and trialkoxide products with low polyalkyl contamination. The following reaction calorimetric data are given in some examples: Maximum achievable temperature: MAT ( ^o C) Heat of reaction: ΔH _r (kilojoules/mol) Heat conversion percentage: TC (%)

Example 1. CH ₃ CH ₂ CH ₂ Sn(N(CH ₂ CH ₃ ) ₂ ) ₃ and CH ₃ CH ₂ CH ₂ Sn(OC(CH ₃ ) ₂ CH ₂ CH ₃ ) ₃ Preparation

This example demonstrates the synthesis of n-propyltin triamine CH ₃ CH ₂ CH ₂ Sn(N(CH _{2 CH 3} ) ₂ ) ₃ , abbreviated as n-PrSn(NEt ₂ ) ₃ , and subsequently converted to n-propyltin trialkoxide CH ₃ CH ₂ CH ₂ Sn(OC(CH ₃ ) ₂ CH ₂ CH ₃ ) ₃ , abbreviated is n-PrSn(O-tAm) ₃ .

( a ) CH ₃ CH ₂ CH ₂ Sn(N(CH ₂ CH ₃ ) ₂ ) ₃ synthesis

Diethylamine (175 mmol, Aldrich) and anhydrous diethyl ether (53 ml, Aldrich) were added with N ₂ under positive N ₂ (g) pressure in a bottle equipped with a bubbling outlet. Mix in a 400 ml reactor. The reactor was cooled to 0 °C and 150 mmol n-butyllithium (Aldrich, 1.6 M in hexanes) was added dropwise. After stirring for 30 minutes, the intermediate product _LiNEt2 was formed and repeated samples were used for characterization. _SnCl2 in tetrahydrofuran (50 mL, 1 M, Fisher) was then added dropwise to the solution. The reactor was heated to 18°C and stirred for 30 minutes. The intermediate product LiSn(NEt ₂ ) ₃ was formed and characterized using replicate samples. The solution was cooled again to 0°C and n-propane iodide (75 mmol, Oakwood) was added dropwise. The solution was heated to 18°C and stirred overnight. The volatile components in the solution are then removed under vacuum. Anhydrous pentane (200 ml, Aldrich) was added to the flask and the mixture was filtered through Celite® S (Aldrich). The flask was washed with an additional 200 ml of anhydrous pentane and the mixture was also filtered. The filtrate was concentrated to remove volatile components and then purified by vacuum distillation (250 mTorr, 70 to 76°C) to obtain n-propyltin tris(diethylamine) as a colorless liquid in a yield of 65.4%, i.e. n-PrSn(NEt ₂ ) ₃ .

Reaction calorimetry was performed to evaluate the maximum achievable temperature (MAT), heat of reaction (ΔH _r ), and thermal conversion (TC) for various reaction types. TC corresponds to the relative amount of total heat released during the addition of individual reagents. MAT( ^o C) ΔH _r (kilojoules/mol) TC (%) 1. HNEt ₂ + n-BuLi → LiNEt ₂ 118 -118 99 2. LiNEt ₂ + SnCl ₂ → LiSn(NEt ₂ ) ₃ 37 -216 89 3. LiSn(NEt ₂ ) ₃ + n-PrI → n-PrSn(NEt ₂ ) ₃ twenty three -94 7

Figure 1 shows the ¹¹⁹ Sn NMR spectrum of LiSn(NEt ₂ ) ₃ in benzene-d ₆ . The spectrum shows a single peak at 31.53 ppm. Figure 2 shows the ¹¹⁹ Sn NMR spectrum of n-PrSn(NEt ₂ ) ₃ in benzene-d ₆ . The spectrum shows the following chemical shifts: ¹¹⁹ Sn NMR (149 MHz, benzene- _d6 ) δ 17.35, -43.75, -68.88. The peak at -43.75 ppm accounts for 99% of the peak integration and is associated with the high purity monoalkyltin triamine product. Figure 3 shows the ¹ H NMR spectrum of n-PrSn(NEt ₂ ) ₃ in benzene-d ₆ . The spectrum shows the following chemical shifts: ¹ H NMR (400 MHz, benzene- d ₆ ) δ 3.08 – 2.88 (m, 6H, -N-CH ₂ -), 1.67 – 1.53 (m, 1H, -Sn-CH ₂ -CH ₂ -), 1.11 – 0.89 (m, 11H, -CH ₃ ).

( b ) converted into CH ₃ CH ₂ CH ₂ Sn(OC(CH ₃ ) ₂ CH ₂ CH ₃ ) ₃

n-Propyltritin (diethylamine) (31.4 mmol) from step (a) of Example 1 was added to a 50 ml round bottom flask equipped with a stir bar. The flask was cooled to 0°C in an ice bath, and tertiary pentanol (97.3 mmol, Aldrich) was slowly added dropwise. The reaction was then warmed to room temperature and stirred for 30 minutes. The volatile components in the solution were removed under vacuum, and the crude product was purified by vacuum distillation (400 mTorr, 65 to 70°C) to yield n-PrSn(O-tAm) ₃ as a colorless oil in 81% yield. .

Figure 4 shows the ¹¹⁹ Sn spectrum of n-PrSn(O-tAm) ₃ in benzene-d ₆ . The spectrum shows the following chemical shifts: ¹¹⁹ Sn NMR (149 MHz, Benzene- _d6 ) δ -195.65. This single peak is consistent with a single tin environment and therefore a monoalkyltin product. Figure 5 is the ¹ H spectrum of n-PrSn(O-tAm) ₃ in benzene-d ₆ with the following chemical shifts: ¹ H NMR (400 MHz, benzene- d ₆ ) δ 1.65 (hept, J = 7.5 Hz, 1H), 1.45 (qd, J = 7.5, 1.8 Hz, 3H), 1.30 – 1.17 (m, 9H), 0.96 (d, J = 7.2 Hz, 1H), 0.94 – 0.78 (m, 5H). Perform quantitative proton tin NMR and proton NMR using selected standards to assess product purity. ¹¹⁹ Sn qNMR, standard CH ₃ Sn(C ₆ H ₆ ) ₃ , purity 94.2 (7) mol% monoalkyl tin; ¹ H qNMR, standard 1,3,5-trimethoxybenzene, purity 95.60 ( 2) Mol% monoalkyl tin.

Example 2. CH ₃ CH ₂ Sn(N(CH ₂ CH ₃ ) ₂ ) ₃ and CH ₃ CH ₂ Sn(OC(CH ₃ ) ₂ CH ₂ CH ₃ ) ₃ Preparation

This example demonstrates the synthesis of ethyltin triamine CH ₃ CH ₂ Sn(N(CH ₂ CH ₃ ) ₂ ) ₃ via a tin oxide reaction involving SnCl ₂ , diethylamine, n-butyllithium, and ethyl iodide. , abbreviated as EtSn(NEt ₂ ) ₃ , and subsequently converted to ethyltin trialkoxide CH ₃ CH ₂ Sn(OC(CH ₃ ) ₂ CH ₂ CH ₃ ) ₃ , abbreviated as EtSn(O-tAm) ₃ .

( a ) CH ₃ CH ₂ Sn(N(CH ₂ CH ₃ ) ₂ ) ₃ synthesis

Diethylamine (1442 mmol, Aldrich) and anhydrous diethyl ether (437 ml, Aldrich) were mixed in a 3-liter round-bottomed flask with N ₂ flow under positive N ₂ (g) pressure; The flask was equipped with a bubble outlet and a reduced pressure outlet to support a continuous flow of _N2 (g). The reactor was cooled to 0 °C in an ice-water bath, and 1236 mmol n-butyllithium (Aldrich, 1.55 M in hexane) was added dropwise. After stirring for 1 hour, the intermediate product LiNEt ₂ was formed, and duplicate samples were prepared for characterization. Then, SnCl ₂ in tetrahydrofuran (412 mL, 1 M, Fisher Co.) was added dropwise to the solution and stirred for 1 hour. The intermediate product LiSn(NEt ₂ ) ₃ was formed, and duplicate samples were prepared for characterization. Ethyl iodide (618 mmol, Aldrich) was then added dropwise and the reaction was allowed to warm to room temperature and stirred overnight. Remove volatile components from the solution under vacuum. Two 500 ml portions of anhydrous pentane were added to the flask and filtered through Celite® S (Aldrich). The filtrate was concentrated to remove volatile components, and then purified by vacuum distillation (60 mTorr, 80 to 85°C) to obtain ethyltin [tris(diethylamine)] as a colorless liquid in a yield of 78.6%, namely EtSn(NEt ₂ ) ₃ .

Figure 6 shows the ¹¹⁹ Sn NMR spectrum of EtSn(NEt ₂ ) ₃ . The spectrum shows the following chemical shifts: ¹¹⁹ Sn NMR (149 MHz, Benzene- _d6 ) δ -40.69. The single peak at -40.69 ppm is related to the high purity of the monoalkyltin triamine product.

( b ) converted into CH ₃ CH ₂ Sn(OC(CH ₃ ) ₂ CH ₂ CH ₃ ) ₃

Ethyltin [tris(diethylamine)] (324 mmol) from step (a) of Example 2 was added to a 400 ml reactor containing 50 ml of pentane. The flask was cooled to 0°C using a cooler, and tertiary pentanol (1004 mmol, Aldrich) was slowly added dropwise. The reaction was warmed to room temperature and stirred for 30 minutes. The volatile components in the solution were removed under vacuum, and the crude product was purified by vacuum distillation (40 mTorr, 82 to 88°C) to yield EtSn(O-tAm) ₃ as a colorless oil in 97% yield.

Figure 7 shows the ¹¹⁹ Sn NMR spectrum of EtSn(O-tAm) ₃ in benzene-d ₆ . _The spectrum shows the following chemical shifts: ¹¹⁹ Sn NMR (149 MHz, Benzene- d6 ) δ -194.24. This single peak is consistent with a single tin environment and therefore a monoalkyltin product. Quantitative proton tin NMR and proton NMR were performed using selected standards to assess product purity. ¹¹⁹ Sn qNMR, standard CH ₃ Sn(C ₆ H ₆ ) ₃ , purity 95.5 (8) mol% monoalkyl tin; ¹ H qNMR, standard 1,3,5-trimethoxybenzene, purity 96.8 ( 1) Mol% monoalkyl tin.

The thermal behavior of the reactions forming ethyltin triamine and ethyltin trialkoxide is summarized below. MAT( ^o C) ΔH _r (kilojoules/mol) TC (%) 1. LiSn(NEt ₂ ) ₃ + EtI → EtSn(NEt ₂ ) ₃ twenty four -128 27 2. EtSn(NEt ₂ ) ₃ + t-AmOH→ EtSn(O-tAm) ₃ 64 -65 99

Example 3. (CH ₃ ) ₃ CSn(N(CH ₂ CH ₃ ) ₂ ) ₃ and (CH ₃ ) ₃ CSn(OC(CH ₃ ) ₂ CH ₂ CH ₃ ) ₃ Preparation

This example demonstrates the synthesis of tertiary butyltin triamine (CH ₃ ) ₃ CSn(N(CH ₂ CH ₃ ) through a tin oxide reaction involving SnCl ₂ , diethylamine, n-butyllithium, and tertiary butyl iodide. ₂ ) ₃ , abbreviated as t-BuSn(NEt ₂ ) ₃ , and subsequently converted to tertiary butyltin trialkoxide (CH ₃ ) ₃ CSn(OC(CH ₃ ) ₂ CH ₂ CH ₃ ) ₃ , abbreviated as t- BuSn(O-tAm) ₃ .

( a ) (CH ₃ ) ₃ CSn(N(CH ₂ CH ₃ ) ₂ ) ₃ synthesis

Diethylamine (88 mmol, Aldrich) and anhydrous diethyl ether (27 ml, Aldrich) were added with N ₂ flow under positive N ₂ (g) pressure in a 400 ml tank equipped with a bubbling outlet. Mix in the reactor. The reactor was cooled to 0°C and 50 mmol n-butyllithium (Aldrich, 1.6 M in hexane) was added dropwise. After stirring for 30 minutes, the intermediate product LiNEt ₂ was formed and was partially isolated for characterization. _SnCl2 in tetrahydrofuran (28 mL, 1 M, Fisher Co.) was then added dropwise to the solution. The reactor was warmed to 20°C and stirred for 30 minutes. The intermediate product LiSn(NEt ₂ ) ₃ was formed and partially isolated for characterization. The solution was cooled again to 0°C and tertiary butyl iodide (38 mmol, Aldrich) was added dropwise. The solution was heated to 40°C and stirred overnight. The volatile components in the solution are then removed under vacuum. Anhydrous pentane (2 x 60 ml, Aldrich) was added to the flask and the mixture was filtered through Celite® S (Aldrich). The flask was washed with an additional 60 ml of anhydrous pentane and the mixture was filtered. The filtrate was concentrated to remove volatile components, and then purified by vacuum distillation (250 mTorr, 72 to 76°C) to obtain tertiary butyltin tris(diethylamine) as a colorless liquid in a yield of 53%, i.e., t -BuSn(NEt ₂ ) ₃ .

Figure 8 shows the ¹¹⁹ Sn NMR spectrum of t-BuSn(NEt ₂ ) ₃ in benzene-d ₆ . The spectrum shows the following chemical shifts: ¹¹⁹ Sn NM (149 MHz, benzene- d ₆ ) δ -81.69. The sharp single peak at -81.69 ppm is related to the high purity monoalkyltin triamine product. No additional peaks were found after triamine distillation.

( b ) converted into (CH ₃ ) ₃ CSn(OC(CH ₃ ) ₂ CH ₂ CH ₃ ) ₃

Tertiary butyltin tris(diethylamine) (13.2 mmol) from step (a) of Example 3 was added to a 50 ml round bottom flask equipped with a stir bar. The flask was cooled to 0°C in an ice bath, and tertiary pentanol (41 mmol, Aldrich) was slowly added dropwise. The reaction was then warmed to room temperature and stirred for 30 minutes. The volatile components in the solution were removed under vacuum, and the crude product was purified by vacuum distillation (60 mTorr, 90°C) to produce t-BuSn(O-tAm) ₃ as a colorless oil in 94% yield.

Figure 9 shows the ¹¹⁹ Sn spectrum of t-BuSn(O-tAm) ₃ in benzene-d ₆ . The spectrum shows the following chemical shifts: ¹¹⁹ Sn NMR (149 MHz, benzene- _d6 ) δ -219.45, -241.08, -369.97. The peak at -219.45 ppm has an integration of 0.0018 and is not related to the dialkyl product. The peak integration at -241.08 ppm is 0.9897, consistent with the monoalkyl t-BuSn(O-tAm) ₃ product. The peak integration at -369.97 ppm is 0.0086 and is attributed to Sn(O-tAm) ₄ .

The NMR results clearly demonstrate the ability to selectively synthesize monoalkyltin triamine and trialkoxide products.

Example 4. (NC(CH ₃ ) ₂ C)Sn(N(CH ₂ CH ₃ ) ₂ ) ₃ Preparation

This example demonstrates the synthesis of isobutyronitrile tin triamine (NC(CH ₃ ) ₂ C by a tin oxide reaction involving SnCl ₂ , diethylamine, n-butyllithium, and 2-bromo-2-methylpropionitrile. )Sn(N(CH ₂ CH ₃ ) ₂ ) ₃ , abbreviated as (NC(CH ₃ ) ₂ C)Sn(NEt ₂ ) ₃ .

Diethylamine (87.5 mmol, Aldrich) and anhydrous diethyl ether (26.5 ml, Aldrich) were placed in a 250 ml round-bottomed flask equipped with a bubbling vacuum outlet under a flow of N ₂ (g). mix. The reactor was cooled to 0 °C in an ice-water bath, and 75 mmol n-butyllithium (Aldrich, 2.53 M in hexane) was added dropwise. After stirring for 30 minutes, SnCl ₂ in tetrahydrofuran (25 mL, 1 M, Fisher Co.) was added dropwise to the solution and stirred for 1 hour. Then, 2-bromo-2-methylpropionitrile (37.5 mmol, synthesized in-house) was added. The reaction was warmed to room temperature and stirred for 1 hour. Volatile solution components were removed under vacuum. Two 100 ml portions of anhydrous pentane were added to the flask and filtered through Celite® S (Aldrich). The filtrate was concentrated to remove volatile components and then purified by vacuum distillation (250 mTorr, 70 to 76°C) to obtain tin tris(diethylamine) isobutyronitrile as a yellow oil in a yield of 21%.

Figure 10 shows the ¹¹⁹ Sn NMR spectrum of (NC(CH ₃ ) ₂ C)Sn(NEt ₂ ) ₃ in benzene-d ₆ . Before acquiring the ¹¹⁹ Sn NMR spectrum shown in Figure 10, the filtrate was concentrated to remove all volatile components. The spectrum shows a primary singlet and a secondary singlet with the following chemical shifts: ¹¹⁹ Sn NMR (149 MHz, Benzene- d ₆ ) δ -94.73, -120.28.

Example 5. (CH ₃ OCH ₂ )Sn(CCSi(CH ₃ ) ₃ ) ₃ Preparation

This example demonstrates the synthesis of methoxymethyltin triacetylide (CH ₃ OCH ₂ )Sn via a tin oxide reaction involving trimethylsilyl acetylene, SnCl ₂ , n-butyllithium, and chloromethyl methyl ether. (CCSi(CH ₃ ) ₃ ) ₃ , abbreviated as (CH ₃ OCH ₂ )Sn(CCSiMe ₃ ) ₃ or MOMSn(CCTMS) ₃ .

Trimethylsilyl acetylene (248 mmol, Oakwood Company, abbreviated as "HCCTMS") and anhydrous diethyl ether (123 ml, Aldrich Company) were placed in a 400 ml reactor equipped with a vacuum bubbler. Mix under flowing N ₂ (g) to create positive N ₂ pressure. The reactor was cooled to 0 °C using a cooler, and 240 mmol n-butyllithium (Aldrich, 1.64 M in hexanes) was slowly added dropwise. After stirring for 30 minutes, the intermediate product LiCCSiMe ₃ , also abbreviated as LiCCTMS, was formed, and repeated samples were prepared for characterization. _SnCl2 in tetrahydrofuran (80 mL, 1 M, Fisher Co.) was then added dropwise to the solution. The solution was stirred at room temperature for 2 hours. The intermediate product LiSn(CCSiMe ₃ ) ₃ , also abbreviated as LiSn(CCTMS) ₃ , was formed, and repeated samples were prepared for characterization. The reactor was then cooled to 0°C using a cooler, and then chloromethyl methyl ether (88 mmol, Aldrich, abbreviated as "MOM-Cl") was added dropwise, and then stirred at room temperature overnight. Remove volatile components from the solution under vacuum. Two 200 ml portions of anhydrous pentane were added to the flask and filtered through Celite® S (Aldrich). The filtrate was concentrated to remove volatile components (250 mTorr, 70 to 76°C) to obtain methoxymethyltin tris(trimethylsilyl acetylide), MOMSn(CCTMS) ₃ , as a white powder, yield 31 %.

Figure 11 shows the ¹¹⁹ Sn NMR spectrum of LiSn(CCSiMe ₃ ) ₃ in benzene-d ₆ . The spectrum shows a single peak at -478.5 ppm. Figure 12 shows the ¹¹⁹ Sn NMR spectrum of (CH ₃ OCH _{2 )} Sn(CCSiMe ₃ ) ₃ in benzene-d 6 with the following chemical shifts: ¹¹⁹ Sn NMR (149 MHz, benzene- d ₆ ) δ - 324.23. A single sharp peak at -324.23 ppm is associated with the high purity monoalkyltin triacetylide product.

Thermal behavior of reactions forming various products is summarized below. MAT( ^o C) ΔH _r (kilojoules/mol) TC (%) 1. HCCTMS+ n-BuLi → LiCCCTMS 98 -160 99 2. LiCCTMS + SnCl ₂ → LiSn(CCTMS) ₃ 27 -177 100 3. LiSn(CCTMS) ₃ + MOM-Cl → MOMSn(CCTMS) ₃ 10 -67 86

Example 6. (NC(CH ₃ ) ₂ C)Sn(CCSi(CH ₃ ) ₃ ) ₃ Preparation

This example demonstrates _the synthesis of isobutyronitrile tin triacetylide (NC(CH ₃ ) ₂ C)Sn(CCSi(CH ₃ ) ₃ ) ₃ , abbreviated as (NC(CH ₃ ) ₂ C)Sn(CCSiMe ₃ ) ₃ .

Trimethylsilyl acetylene (232.5 mmol, Oakwood Company) and anhydrous diethyl ether (116 ml, Aldrich Company) were mixed under flowing N ₂ (g) in a 400 equipped with a vacuum bubble outlet. ml reactor. The reactor was cooled to 0 °C using a cooler, and 225 mmol n-butyllithium (Aldrich, 2.53 M in hexane) was added dropwise. After stirring for 30 minutes, the intermediate product LiSnCCSiMe ₃ , also abbreviated as LiCCTMS, was formed, and repeated samples were prepared for characterization. Then, _SnCl2 in tetrahydrofuran (75 mL, 1 M, Fisher Co.) was added dropwise to the solution. The reactor was heated to 20°C and stirred for 1 hour. The intermediate product LiSn(CCSiMe ₃ ), also abbreviated as LiSn(CCTMS) ₃ , was formed, and repeated samples were prepared for characterization. The solution was cooled again to 0°C using a cooler, and ZnBr ₂ (75 mL, 1 M, Aldrich) in THF (Aldrich) was added dropwise. The reaction was stirred for 10 minutes. The intermediate product Li[Zn(Sn(CCTMS) ₃ ) ₃ ] was formed, and additional samples were prepared for characterization. 82.5 mmol of 2-bromo-2-methylpropionitrile (IBN, synthesized in-house) was then added to the reaction. The reactor temperature was maintained at 0°C and stirred overnight. 100 ml of anhydrous pentane was added to the flask and filtered through silica (Aldrich). Wash the flask with another 200 ml of anhydrous pentane and then filter. The filtrate was concentrated to remove volatile components, producing a viscous, off-white, semi-solid form of isobutyronitrile tin tris(trimethylsilyl acetylide), (NC(CH ₃ ) ₂ C)Sn, in 76% yield (CCSiMe ₃ ) ₃ .

Figure 13 shows the ¹¹⁹ Sn NMR spectrum of (NC(CH ₃ ) ₂ C)Sn(CCSiMe ₃ ) ₃ in benzene-d ₆ . The spectrum shows the following chemical shifts: ¹¹⁹ Sn NMR (149 MHz, Benzene- d ₆ ) δ -73.55, -151.23, -166.08, -175.87, -264.02, -274.33, -384.39. The main singlet state and the secondary singlet state are at -264.02 and -166.08 respectively, and the peak integrals are 0.75 and 0.17 respectively.

The following summarizes the thermal behavior of reactions involving _ZnBr2 and IBN. MAT( ^o C) ΔH _r (kilojoules/mol) TC (%) 1. LiCCTMS + SnCl ₂ → LiSn(CCTMS) ₃ 16 -97 97 2. LiSn(CCTMS) ₃ +ZnBr ₂ →Li[Zn(Sn(CCTMS) ₃ ) ₃ ] 8 -130 91

The above examples show the NMR spectrum of the synthesized organotin compound, which does not show any peaks related to polyalkyltin compounds.

Example 7. (CH ₃ ) ₂ ICSn(N(CH ₂ CH ₃ ) ₂ ) ₃ and (CH ₃ ) ₂ ICSn(OC(CH ₃ ) ₃ ) ₃ Preparation

This example demonstrates the synthesis of iodopropyltintriamine (CH ₃ ) ₂ through a tin oxide reaction involving SnCl ₂ , diethylamine, n-butyllithium, tertiary potassium butoxide, and 2,2-diiodopropane. ICSn(N(CH ₂ CH ₃ ) ₂ ) ₃ , abbreviated as 2-iodo-PrSn(NEt ₂ ) ₃ , and its subsequent conversion to 2-iodopropyltin tri(tertiary butoxide), i.e. (CH ₃ ) ₂ ICSn(OC(CH ₃ ) ₃ ) ₃ , abbreviated as iodine PrSn(O-tBu) ₃ .

n-Butyllithium (1.03 mL, 2.53 mmol, 2.45 M in hexane) was added to a cold solution (-50°C) of diethylamine (0.262 g, 2.53 mmol) in diethyl ether (4 mL). middle. After a few minutes, a slurry of tin(II) chloride (0.160 g, 0.845 mmol) and potassium butoxide tertiary (0.095 g, 0.845 mmol) in THF (4 ml) was added. The contents were heated to 0°C and stirred for 2 hours. The flask was re-cooled to -50°C and 2,2-diiodopropane (0.25 g, 0.845 mmol) was added. The resulting reaction mixture was allowed to warm to room temperature over 16 hours, at which time the solvent was removed in vacuo. The product 2-iodopropyltin tris(diethylamine) was recrystallized from pentane and tertiary butanol (3.1 eq.) was added. The trialkoxide product was distilled under dynamic vacuum at 60°C and further purified by fractional distillation. The ¹¹⁹ Sn NMR spectrum and ¹ H NMR spectrum of the isolated product are shown in Figure 14 and Figure 15 respectively.

Example 8. (C ₆ H ₄ I)CH ₂ Sn(CCSi(CH ₃ ) ₃ ) ₃ and (C ₆ H ₄ I)CH ₂ Sn(OC(CH ₃ ) ₃ ) ₃ Preparation

This example _demonstrates the synthesis of iodobenzyltin triacetylide (C ₆ H ₄ I)CH ₂ Sn(CCSi(CH ₃ ) ₃ ) ₃ , abbreviated as 3-iodobenzylSn(CCSiMe ₃ ) ₃ , subsequently converted to 3-iodobenzyltin tri(tertiary butoxide), That is (C ₆ H ₄ I)CH ₂ Sn(OC(CH ₃ ) ₃ ) ₃ , abbreviated as iodobenzyl Sn(O-tBu) ₃ .

n-Butyllithium was added to a cold (-50°C) solution of trimethylsilylacetylene (TMSA) in diethyl ether. After a few minutes, a slurry of tin(II) chloride and tertiary potassium butoxide in THF was added. Stir contents while heating to room temperature for at least 2 hours. The newly formed putative intermediate potassium tris(trimethylsilyl acetylide)stannane was slowly added to a cold (-50°C) solution of 3-iodobenzyl bromide in THF. After stirring overnight, the solvent was removed in vacuo and the product was extracted with pentane. The salts were removed by filtration and the pentane was removed in vacuo to give a white semi-solid. Add triethylamine (5.0 equivalents) and tertiary butanol (5.0 equivalents), and heat the solution to 80°C for 40 hours. Excess TEA/tBuOH was removed in vacuo and the trialkoxide product was isolated by distillation. Further purification is achieved by fractional distillation. The ¹¹⁹ Sn NMR spectrum and ¹ H NMR spectrum of the isolated product are shown in Figure 16 and Figure 17 respectively.

This application claims priority over the application filed on August 2, 2020 and entitled "Methods to Produce Monoalkyl Tin Compositions Wit" granted to Edson et al. The co-pending U.S. Provisional Patent Application 63/070,098 filed on May 21, 2021, entitled "High EUV Absorption Organotin Patterning" was granted to Cardineau et al. "High EUV Absorption Organotin Patterning Compositions and Coatings" is a co-pending U.S. Provisional Patent Application No. 63/191,646, both of which are incorporated herein by reference.

The above embodiments are intended to be illustrative and not limiting. Other embodiments are within the scope of the patent claims. Furthermore, although the invention has been described with reference to specific embodiments, those skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. Any incorporation by reference of the above documents is expressly limited such that no matter contrary to the express disclosures herein will be incorporated. To the extent that specific structures, compositions, and/or processes are described herein as having components, elements, components, or other subdivisions, it should be understood that, unless otherwise specifically stated, the disclosure herein encompasses such specific implementation aspects; including such Embodiments of specific components, components, components, other subdivisions, or combinations thereof; and implementations consisting essentially of such specific components, components, or other subdivisions, or combinations thereof, these embodiments may include unchanged Additional features of the underlying nature of the subject matter, as suggested in the discussion. The term "about" is used herein to refer to the expected uncertainty of the associated value, as understood in the particular context by one of ordinary skill in the art.

without

Figure 1 is the ¹¹⁹ Sn NMR spectrum of LiSn(NEt ₂ ) ₃ in benzene-d ₆ .

Figure 2 shows the ¹¹⁹ Sn NMR spectrum of n-PrSn(NEt ₂ ) ₃ in benzene-d ₆ .

Figure 3 shows the ¹ H NMR spectrum of n-PrSn(NEt ₂ ) ₃ in benzene-d ₆ .

Figure 4 shows the ¹¹⁹ Sn NMR spectrum of n-PrSn(O-tAm) ₃ in benzene-d ₆ .

Figure 5 shows the ¹ H NMR spectrum of n-PrSn(O-tAm) ₃ in benzene-d ₆ .

Figure 6 is the ¹¹⁹ Sn NMR spectrum of EtSn(NEt ₂ ) ₃ in benzene-d ₆ .

Figure 7 is the ¹¹⁹ Sn NMR spectrum of EtSn(O-tAm) ₃ in benzene- _{d 6} .

No. 8 is the ¹¹⁹ Sn NMR spectrum of t-BuSn(NEt ₂ ) ₃ in benzene-d ₆ .

Figure 9 shows the ¹¹⁹ Sn NMR spectrum of t-BuSn(O-tAm) ₃ in benzene-d ₆ .

Figure 10 is the ¹¹⁹ Sn NMR spectrum of (NC(CH ₃ ) ₂ C)Sn(NEt ₂ ) ₃ in benzene-d ₆ .

Figure 11 is the ¹¹⁹ Sn NMR spectrum of LiSn(CCSiMe ₃ ) ₃ in benzene-d ₆ .

Figure 12 is the ¹¹⁹ Sn NMR spectrum of (CH ₃ OCH ₂ )Sn(CCSiMe ₃ ) ₃ in benzene-d ₆ .

Figure 13 is the ¹¹⁹ Sn NMR spectrum of (NC(CH ₃ ) ₂ C)Sn(CCSiMe ₃ ) ₃ in benzene-d ₆ .

Figure 14 shows the ¹¹⁹ Sn NMR spectrum of 2-iodopropyltin tris(tert-butoxide); 2IP.

Figure 15 shows the ¹ H NMR spectrum of 2IP.

Figure 16 shows the ¹¹⁹ Sn NMR spectrum of 3-iodobenzyltin tris(tert-butoxide) (IBT).

Figure 17 shows the ¹ H NMR spectrum of IBT.

Claims (13)

A blend composition comprising a first compound represented by _RSnL3 , wherein _R is a hydrocarbyl group having 1 to 31 carbon atoms, and L is a hydrolyzable ligand or _O & _{lt ;} A hydrocarbyl group with an optional unsaturated carbon-carbon bond, an optional aromatic group, and an optional heteroatom, and R" is a hydrocarbon group having 1 to 31 carbon atoms and substituted with one or more heteroatoms, wherein L is not ( _C≡CSiR'3 ), (2) A halogenated alkyltin compound represented by the formula R'R" _ACSnZ3 , wherein A is a halogen atom (F, Cl, Br, or I) or has at least one halogen substitution An aromatic ring of a base, wherein R' and R'' are independently H, halogen, or having 1 to 15 carbon atoms and optionally unsaturated carbon-carbon bonds, optional aromatic groups, and optionally hetero A hydrocarbyl group of an atom, and Z is a hydrolyzable ligand or O _x (OH) _3-x , 0＜x＜3, (3) Hydrocarbyl tin represented by the formula R'R"(R'"O)CSnZ ₃ Compounds wherein R', R'' and R'" are independently hydrogen or have from 1 to 15 carbon atoms and optionally unsaturated carbon-carbon bonds, optionally aromatic groups, and optionally heteroatoms Hydrocarbyl, and Z is a hydrolyzable ligand or O _x (OH) _3-x , 0＜x＜3, (4) An alkyltin compound represented by the formula R'R"(N≡C)CSnZ ₃ , where R' and R'' are independently hydrocarbon groups having 1 to 15 carbon atoms and optionally unsaturated carbon-carbon bonds, optional aromatic groups, and optional heteroatoms, and Z is a hydrolyzable complex The base is O _x (OH) _3-x , 0<x<3, or a combination of the above. The blending composition of claim 1, wherein the one or more heteroatoms and/or the optional heteroatoms include N, O, P, S, or halogen atoms. The blending composition of claim 1, wherein the one or more heteroatoms and/or the optional heteroatoms include I. The blending composition of claim 1, wherein the halogen atom or the at least one halogen substituent includes F. The blending composition of claim 1, wherein R contains branched alkyl, aryl, alkenyl, or cyclic groups. The blending composition of claim 1, wherein R includes a hydrocarbon group substituted by a halogenated group, wherein R and R'R"AC, R'R"(R'"O)C, and R'R"( N≡C)C is different. The blending composition of claim 1, wherein the hydrocarbon group of the second compound includes a fully iodinated aryl group. The blending composition of claim 1, wherein the hydrocarbon group of the second compound includes an ether group, a nitrile group, a halogenated group, or a combination thereof. The blending composition of claim 1, wherein the first compound and the second compound form a radiation-sensitive Sn-C bond. The blending composition of claim 1, wherein L includes an alkoxide ligand, an acetylide ligand, an amine ligand, or a dialkylamine ligand. A solution comprising an aprotic organic solvent and the blending composition of any one of claims 1 to 10, the solution having a tin concentration of 0.0001 M to 1 M. A coated substrate comprising: A substrate has a surface, and at least a part of the substrate has an organic metal material, wherein the organic metal material includes the blending composition according to any one of claims 1 to 10. The coated substrate of claim 12, wherein the organic metal material forms a coating with an average thickness of about 1 nanometer to 50 nanometers.